This invention relates to reactive dyes containing a halobenzene nucleus and, in particular, reactive dyes of this type containing two or more reactive components.
Dyes are known which contain a halobenzene nucleus linked via an azo group to another aromatic nucleus such that the halobenzene nucleus forms part of the chromophoric chain (see for example GB-A-882001). Dyes of this type which contain two such halobenzene nuclei are disclosed in CA64,14316d (1966), which is an English language abstract of an article by Matsui et al, Yuki Gosei Kagaku Kyokai Shi (1966), 24(2), 132-136.
Dyes are also known in which the halobenzene nucleus is attached to a chromophoric group by a sulphonamide or amide linkage; see, for example, GB-A-978162 and CA59,12949g (1963), which is an English language abstract of an article by Matsui et al in Yuki Gosei Kagaku Kyokai Shi (1962), 20,1100-1112. Again dyes of this type may contain two such halobenzene nuclei; see GB-A-978162.
In other known dyes the halobenzene nucleus is linked to a chromophoric group by an amine linkage; see U.S. Pat. No. 3,301,847 and CA61,16193f (1964) which is an English language abstract of an article by Matsui et al in Kogyo Kagaku Zasshi, (1964), 67(1),94-97. However, such dyes contain only one reactive group.
We have now found surprisingly that dyes having at least one halobenzene nucleus linked to a chromophoric group via an amino linkage and additionally containing a second reactive group have particularly high build up, especially in warm dyeing applications.
According to the invention there is provided a dye containing
at least one chromophore D;
at least a first, halobenzene, reactive group Z1, of the formula (I) 
in which:
n is 1 or 2
X, or each X independently, is an electron withdrawing group; and
Y is a halogen atom;
at least a second reactive group Z2 selected from
(1) a group of the formula (I), given and defined above, but selected independently thereof;
(2) a group of the formula (II) 
wherein
m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0;
Y1, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and
T is C1-4alkoxy, C1-4thioalkoxy or N(R1)(R2), in which each of R1 and R2 independently is hydrogen, optionally substituted C1-4alkyl or optionally substituted aryl;
(3) a group of the formula (III) 
wherein:
x is 1, 2 or 3; y is zero, 1 or 2; and
x+yxe2x89xa63;
Y2, or each Y2 independently, is a halogen atom or an optionally substituted pyridinium group; and
U or each U independently, is C1-4alkyl or C1-4alkylsulphonyl;
(4) a group of the formula (IV)
xe2x80x94SO2CH2CH2X1xe2x80x83xe2x80x83(IV)
wherein X1 is an eliminatable group;
(5) a group of the formula (V)
xe2x80x94SO2(CH2)zCHxe2x95x90CH2xe2x80x83xe2x80x83(V)
wherein z is zero or 1; and
(6) a group of formula (VI)
xe2x80x94Wxe2x80x94C(R10)xe2x95x90CH2xe2x80x83xe2x80x83(VI)
wherein:
R10 is hydrogen, C1-4alkyl or halogen; and
W is xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94N(R11)C(xe2x95x90O)xe2x80x94 in which R11 is hydrogen or C1-4 alkyl;
at least a first linking group L1, linking the said first, halobenzene, reactive group Z1 to one of components (i) the or a chromophore D and (ii) the second reactive group Z2, which said first linking group L1 presents an amino nitrogen to the reactive group Z1 and to the component (i) or (ii) or, when component (i) contains a heterocyclic nitrogen atom, is linked directly to the nitrogen atom and which said first linking group L1 optionally includes a hydrocarbon bridging group, which hydrocarbon bridging group B has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero atom and is optionally a chromophore; and
when Z2 is selected from the said groups (I)-(III), at least a second linking group L2 linking the second reactive group Z2 to one of (i) the or a chromophore D and (ii) the said first reactive group Z1, which said linking group L2 is selected from
(1) a linking group L1, but selected independently thereof; or
(2) an amide linkage; and
(3) a sulphonamide linkage; and
optionally at least one aromatic group Ar which, when Z2 is selected from the said groups (IV)-(VI), may carry the said reactive group Z2.
Preferably, the linking group L1 has the formula (VII)1 
N(R)xe2x80x83xe2x80x83(VII)1
wherein R is hydrogen or optionally substituted C1-4alkyl, such that the same amino group presents itself to each of the reactive group Z1 and the component (i) or (ii), as defined above; or
is a piperazinoalkylamino group of the formula (VII)2 
wherein each R, independently, is as defined above, such that respective amino nitrogens, one of the piperazine group and the other of the alkylamino group, present themselves respectively, to the reactive group Z1 and to the component (i) or (ii), as defined above; or
has the formula (VII)3 
xe2x80x94N(R)BN(R)xe2x80x94xe2x80x83xe2x80x83(VII)3
wherein B is a hydrocarbon bridging group as defined above, each R, independently, is as defined above and B is optionally linked additionally to at least one additional group xe2x80x94N(R).
The hydrocarbon bridging group B may be a straight or branched, optionally substituted, C2-6alkylene group optionally interrupted by at least one hetero atom, for example, O, S or N. Optional substituents are OH alkoxy, carboxy, carboxylic ester or carboxamide. Alternatively the bonding group B may be an optionally substituted arylene especially phenylene group. Optional substituents are SO3H and salts thereof, C1-4alkyl, C1-4alkoxy and chloro. The bridging group B is especially preferably an optionally substituted aryl group.
An especially preferred dye embodying the invention has the formula (VIII)
Z1xe2x80x94L1xe2x80x94Dxe2x80x94(L2)axe2x80x94Z2xe2x80x83xe2x80x83(VIII)
wherein:
D is a chromophore;
each of L1 and L2 is an amine or piperazine linkage of the formula
xe2x80x94N(R)xe2x80x94 (VII)1; 
wherein:
R, or each R independently, is hydrogen or C1-4 alkyl;
B is a hydrocarbon bridging group which has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero atom and is optionally a chromophore;
a is zero or 1; and
b is from 2 to 6 inclusive;
Z1 is a group 
in which:
n is 1 or 2;
X, or each X independently, is an electron withdrawing group; and
Y is a halogen atom; and
when a is 1, Z2 is:
a group of the formula (I), given and defined above but selected independently thereof; or
a group of the formula (II) 
wherein:
m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0;
Y1, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and
T is C1-4 alkoxy, thioalkoxy or N(R1)(R2) in which R1 is hydrogen, optionally substituted C1-4 alkyl or optionally substituted aryl and
R2 is hydrogen or optionally substituted C1-4 alkyl; or
a group of the formula (III) 
wherein:
x is 1, 2 or 3; y is zero, 1 or 2; and x+yxe2x89xa63;
Y2, or each Y2 independently, is a halogen atom; and
U, or each U independently, is C1-4 alkyl or C1-4 alkylsulphonyl; and
when a is zero, Z2 is:
xe2x80x94SO2CH2CH2X1xe2x80x83xe2x80x83(IV)
in which X1 is an eliminatable group; or
xe2x80x94SO2(CH2)zCHxe2x80x94CH2xe2x80x83xe2x80x83(V)
wherein
z is zero or 1; or
a group of formula (VI)
xe2x80x94Wxe2x80x94C(R10)xe2x95x90CH2xe2x80x83xe2x80x83(VI)
wherein:
R10 is hydrogen, C1-4alkyl or halogen; and
W is xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94N(R11)C(xe2x95x90O)xe2x80x94 in which R11 is hydrogen or C1-4 alkyl.
In the halobenzene nucleus of the formula (I), X or each X independently, may be selected from nitro, cyano, alkylsulphonyl, dialkylaminosulphonyl and sulphonic acid groups and salts thereof. Preferably, X or each X independently, is selected from nitro and cyano.
The halogen atom in the halobenzene nucleus of formula (I) is preferably fluorine or chlorine.
The group R in the linking group L1 of formulae (1)-(3) may be any of hydrogen, methyl, ethyl, n- or i-propyl or n-, s- or t-butyl, but is preferably hydrogen.
In the dye of formula (VII), each of Z1 and Z2, independently, is preferably a group of the above mentioned formula (I). Moreover, it is even more preferred that each of Z1 and Z2 is the same group as the other.
However, alternatively, Z1 may be a halobenzene nucleus of the formula (I), A may be zero and Z2 a group of the formula
xe2x80x94SO2CH2CH2X1xe2x80x83xe2x80x83(IV)
in which X1 is an eliminatable group such as OSO3H, OPO3H2 and salts of any of these, and Cl, a preferred group (IV) being
xe2x80x94SO2CH2CH2OSO3H
(or a salt thereof)
or 
xe2x80x94SO2(CH2)zCHxe2x95x90CH2xe2x80x83xe2x80x83(V)
wherein z is zero or 1.
In an other alternative range of dyes, Z1 is a halobenzene nucleus of the formula (I) above and Z2 is a halotriazine nucleus of the formula (II) 
wherein m is 1 or 2, p is 0 or 1,
when m is 1, p is 1 and
when m is 2, p is 0;
Y1, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and
T is C1-4 alkoxy, C1-4thioalkoxy or N(R1)(R2) in which R1 is hydrogen, optionally substituted C1-4alkyl or optionally substituted aryl; and
R2 is hydrogen or optionally substituted C1-4alkyl.
In the above formula (II), Y1 is preferably fluorine, chlorine or optionally substituted pyridinium which may be derived from, for example, nicotinic or isonicotinic acid or their carboxamides.
Each of R1 and R2 is preferably hydrogen, but at least one of R1 and R2 may be a C1-4 alkyl group and indeed R1 may additionally be an optionally substituted aryl, preferably phenyl, group.
When such a C1-4 alkyl or aryl group is substituted, a preferred substituent is hydroxyl, amino, halo, carboxy or sulpho.
In yet another alternative dye in accordance with the invention, Z1 is a halobenzene nucleus of the formula (I) and Z2 is a halopyrimidine nucleus of the formula 
wherein
x is 1, 2 or 3; y is 0, 1 or 2; and x+yxe2x89xa63;
Y2, or each Y2 independently, is halogen atom; and
U, or each U independently, is C1-4alkyl or C1-4alkylsulphonyl.
In the above formula (III) Y2 is preferably fluorine or chlorine.
A preferred range of dyes embodying the invention has the formula (XXX)
Z1xe2x80x94L1xe2x80x94D[L3]qxe2x80x94[Z3xe2x80x94L4r[J1]s[L2]aZ2[L5xe2x80x94J2]txe2x80x83xe2x80x83(XXX)
wherein:
Z3 is a third reactive group selected from the groups of the formulae (I)-(III), given and defined above;
each of J1 and J2, independently, is an optionally substituted aryl group or a chromophore;
L3 is a linking group linking Z3 and D;
L4 is a linking group linking Z3 and J1;
L5 is a linking group linking Z3 and J2;
each of q, r, s and t independently, is zero or 1;
each of Z1, Z2, L1, L2 and a is as defined above; and
when at least one of a and t is 1, Z2 is selected from the groups of the formulae (I)-(III), given and defined above.
In one such range of dyes, q is 1, r is 1, s is 1, each of a and t is zero and Z2 is selected from the groups of the formulae (IV)-(VI), given and defined above.
In another such range, q is 1, r is 1, s is zero, a is zero and t is 1.
In a dye of the formula (XXX), each of L3 and L4, independently, is preferably selected from one of the groups of the formulae (VII)1, (VII)2 and (VII)3, given and defined above;
each of L3 and L4 is preferably a group of the formulae (VII)1, given and defined above.
In one preferred range of dyes of the formula (XXX), q is 1, r is zero, s is 1, a is zero and t is zero and in such a range L3 is preferably a group of the formula (VII)3 
xe2x80x94N(R)BN(R)xe2x80x94xe2x80x83xe2x80x83(VII)3
wherein B is a triazine group substituted by a non reactive group.
In a dye of the formula (XXX), the chromophore D is preferably an azo chromophore derived from 1-hydroxy-8-aminonaphthalene substituted by at least one sulphonic acid group.
Yet another range of dyes embodying the invention has the formula
Z1xe2x80x94L1xe2x80x94D1[L3xe2x80x94Z3(L4xe2x80x94Z4)lL5xe2x80x94D2]k[L2]aZ2
wherein:
D1 is a first chromophore;
D2 is a second chromophore;
Z3, when present, is a third reactive group selected from the groups of the formulae (I)-(III), given and defined in claim 1;
Z4, when present, is a fourth reactive group selected from the groups of the formulae (I)-(III), given and defined in claim 1;
L3 is a linking group linking Z3 to D1;
L4 is a linking group linking Z3 to Z4;
L5 is a linking group linking D2 to one of Z3 and Z4;
each of k and l, independently, is zero or 1; and
each of Z1, Z2, L1, L2 and a is as defined in claim 1.
In one range of such dye of formula (XXXI), a is 1, Z2 is a group of the formula (I), given and defined above, k is zero and D1 is a tetrakisazo chromophore containing two residues of H-acid linked together by a group forming part of the chromophore.
In another such range, a is 1, each of Z1 and Z2 is a group of the formula (I), given and defined above, each of k and l is 1;
each of D1 and D2 is a disazo chromophore containing a respective residue of H-acid,
each of Z1 and Z4 is a group of the formula (II), given and defined above, and
L4 is a linking group of the formula (VII)2 
or (VII)3, given and defined above.
In still further such ranges
(i) a is 1, Z2 is a group of the formula (I), given and defined above, k is 1 and l is 1; or
(ii) a is 1, Z3 is a group of the formula (I), given and defined above, k is 1 and l is zero.
Yet another preferred range of dyes embodying the invention has the formula (XXXII)
Z1xe2x80x94L1xe2x80x94Z3xe2x80x94L3xe2x80x94Dxe2x80x94Z2xe2x80x83xe2x80x83(XXXII)
wherein:
Z3 is a third reactive group selected from the groups (I)-(III), given and defined above; and
L3 is a third linking group selected from the groups (VII)1, (VII)2 and (VII)3, given and defined above;
Z2 is a second reactive group selected from the groups (IV)-(VI), given and defined above; and
each of Z1 and L1 is as defined above.
In such dyes of the formula (XXXII), L1 is preferably a linking group of the formula (VII)2 or (VII)3, given and defined above and Z3 is preferably a group of the formula (II), given and defined above.
Another range of dyes embodying the invention has the formula (XXXIII)
Other ranges of dyes embodying the invention are of the respective formulae
D2xe2x80x94L2xe2x80x94Z2xe2x80x94L3xe2x80x94D1xe2x80x94L1xe2x80x94Z1xe2x80x83xe2x80x83(XXXIV)
wherein:
each of D1 and D2, independently, is a chromophore;
L3 is a linking group selected from groups of the formula (I)-(III), given and defined above; and
each of Z1, Z2, L1 and L2 is as defined above; and 
wherein:
each of D1 and D2, independently, is a chromophore;
L3 is a linking group selected from the groups of the formulae (I)-(III), given and defined above; and
each of Z1, Z2, L1 and L2 is as defined above; and 
wherein:
one of Z3 and Z4 is a reactive group Z2;
Dxe2x80x94L2xe2x80x94Z2xe2x80x94L1xe2x80x94Z1xe2x80x83xe2x80x83(XXXIII)
wherein:
Z2 is selected from groups of the formulae I-(III), given and defined above; and
each of D, Z1, L1 and L2 is as defined above.
In such dyes of the formula (XXXIII), Z2 is preferably a group of the formula (II), given and defined above and L2 is preferably a linking group selected from the groups (VII)1, (VII)2 and (VII)3, given and defined above, more preferably a group of the formula (VII)2 or (VII)3, given and defined above; and L1 is a group of the formula (VII)3, given and defined above, in which B is an optionally substituted aryl group, or is alternatively a chromophoric bridging group.
In the range of dyes of formulae (XXXII), a preferred chromophore D is a disazo dye containing a residue derived from H-acid and having azo groups at the 2- and 7-positions.
Another preferred chromophore D is a group of the formula 
each of Z3 and Z4, independently, is a reactive group selected from the formulae (IV)-(VI), given and defined above;
each of t and u, independently, is zero or 1 and at least one of t and u is 1;
D is a chromophore;
Ar is an optionally substituted aryl group;
L1 is a group of the formula 
wherein each R, independently, is as defined in claim; and
Z1 is as defined above.
In such dyes of formulae (XXXVI), D is preferably a disazo dye containing a residue derived from H-acid.
In a dye embodying the invention, the or a chromophore D may contain a heterocyclic nitrogen atom, in which case the linking group may have the formula 
wherein each of B, R and b is as defined above and the bond {circle around (1)} is linked to the heterocyclic nitrogen atom of the chromophore.
Such dyes, may have the formula
Z1xe2x80x94L1xe2x80x94DN"Brketopenst"L2"Brketclosest"aZ2"Brketopenst"L5xe2x80x94Ar]t
wherein:
DN is a chromophore containing a heterocyclic group including a nitrogen atom;
L1 is a group of the formula (VII)4 or (VII)5, given and defined above, directly attached via the bond {circle around (1)}, to the nitrogen atom of the said chromophore DN;
Ar is an optionally substituted aryl group;
and each of Z1, Z2, L2, L5, a and t is as defined above.
A typical chromophore D containing a heterocyclic nitrogen atom has the formula 
In the above formulae, wherever L1-L5, J1, J2 or B is or has an optionally substituted phenyl group, optional substituents are SO3H or a salt thereof, C1-4alkyl, especially methyl and chloro, especially SO3H.
Again, in all of the above formulae, where the groups Z2 is any of the groups of the formulae (I)-(III), it is most preferably of the formula (II).
Likewise in all such formulae, where Z2 is any of the groups (IV)-(VI), it is most preferably of the formula (IV) or (V), wherein Z is zero.
In a dye according to the invention, in general, the or each chromophoric group independently preferably comprises an azo (which may be a monoazo, polyazo or metal complex azo), anthraquinone, hydrazone, phthalocyanine, triphenodioxazine or formazan group. Examples of chromophoric groups which may be present are those given as types (a)-(g) of the group xe2x80x9cD1xe2x80x9d in formula (I) of U.S. Pat. No. 5,484,899, which is incorporated herein by reference.
Preferred azo groups are monoazo and disazo groups. Preferred monoazo groups have the formula
xe2x80x94Ar1xe2x80x94Nxe2x95x90Nxe2x80x94Ar2xe2x80x94
wherein Ar1 is an aryl or heteroaryl group and Ar2 is an aryl group.
It is preferred that each aryl group independently is a mono- or di-cyclic aryl group. Preferred aryl groups are optionally substituted phenyl and optionally substituted naphthyl. Preferred heteroaryl groups are pyridonyl and pyrazolonyl.
A first preferred monoazo group is of the Formula (IX) (or salt thereof): 
wherein:
Ar1 is an aryl group, preferably a benzene or naphthalene nucleus;
R3, or each R3 independently, is C1-4 alkyl, nitro, halo or sulphonic acid or a salt thereof;
c is zero or 1 to 4;
R4, or each R4 independently, is a sulphonic acid or a salt thereof; and
d is 1 or 2;
and is more preferably of the formula: 
wherein each of Ar1, R3 and a are as defined above, R4 is sulpho and c is zero or 1.
Ar1 is preferably optionally substituted phenyl or naphthyl, especially a phenyl or naphthyl group having at least one sulpho substituent. Further optional substituents which may be present on Ar include a halogen atom, especially chlorine; an alkyl radical, especially C1-4 alkyl, more especially methyl; an acylamido radical, especially acetylamino, benzamido or sulphonated benzamido; amino; hydroxy; and an alkoxy radical, especially C1-4 alkoxy, more especially methoxy.
As examples of phenyl groups having at least one sulpho substituent there may be mentioned 2-, 3- or 4-sulphophenyl; 2-sulpho-4-nitrophenyl; 2-sulpho-5-nitrophenyl; 4-sulpho-2-methylphenyl; 5-sulpho-2-methylphenyl; 2-sulpho-4-methylphenyl; 5-sulpho-2-methoxyphenyl; 2-sulpho-4-methoxyphenyl; 4-sulpho-2-chlorophenyl; 5-acetamido-2-sulphophenyl; 5-sulpho-2-carboxyphenyl; 2,4-disulphophenyl; 2,5-disulphophenyl; and 3,5-disulphophenyl.
As examples of naphthyl groups having at least one sulpho substituent there may be mentioned 1-sulphonaphth-2-yl; 1,5-disulphonaphth-2-yl; 1,5,7-trisulphonaphth-2-yl; 3,6,8-trisulphonaphth-2-yl; 5,7-disulphonaphth-2-yl; 6-sulphonaphth-2-yl; 4-,5-,6-, or 7-sulphonaphth-1-yl; 4,8-disulphonaphth-1-yl; 3,8-disulphonaphth-1-yl; 2,5,7-trisulphonaphth-1-yl; and 3,5,7-trisulphonaphth-1-yl.
Preferred optional substituents which may be present on the naphthalene nucleus of Formula (IX) are those mentioned above for Ar1.
Groups of the Formula (IX) are preferably linked to a group L1 or L2 at the 6-, 7- or 8-position, especially the 6- or 8-position. When L1 or L2 is to be linked at the 8-position, it is preferred that R5 is a sulpho group at the 5- or 6-position.
Thus a preferred monoazo dye embodying the invention has the formula (XVII) 
wherein:
each R independently and a is as defined above;
one of Z3 and Z4 is a group Z1 and the other is a group Z2;
the group Z4 is selected from the groups of the formulae (I)-(III), given and defined above.
Ar1 is a benzene or naphthalene nucleus;
R3, or each R3 independently, is C1-4 alkyl, nitro, halo or sulphonic acid or salt thereof;
c is zero or 1-4;
R4, or each R4 independently, is a sulphonic acid or a salt thereof; and
d is 1 or 2.
A preferred disazo group is of the Formula (XI) (or salt thereof):
Ar1xe2x80x94Nxe2x95x90Nxe2x80x94Mxe2x80x94Nxe2x95x90Nxe2x80x94Exe2x80x83xe2x80x83(XI)
wherein:
M and E are each independently optionally substituted phenylene or naphthalene; and
Ar1 is as defined above.
It is preferred that E is optionally substituted naphthalene and M is optionally substituted phenylene. The optional substituents which may be present on M or E are preferably independently selected from halo, especially chloro; alkoxy, especially C1-4 alkoxy; alkyl, especially methyl; sulpho; carboxy; hydroxy; amino; acylamino, especially acetamido, benzamido and sulphonated benzamido, and pyrimidinylamino or triazinylamino cellulose-reactive groups.
As Examples of groups represented by M and E, there may be mentioned phenylene, 2-methyl-1,4-phenylene, sulphophenylene, ureidophenylene, 7-sulpho-1,4-naphthalene, 6-sulpho-1,4-naphthalene; 8-sulpho-1,4-naphthalene and 6-hydroxy-4-sulpho-1,5-naphthalene.
An especially preferred range of disazo-dyes has the formula (XVIII) 
wherein:
one of Z5 and Z6 is a group Z1 and the other is a group Z2;
each of f and g independently is zero or 1;
when Z5 or Z6 is any of the groups of the formulae (I)-(III), given and defined above, f or g respectively is 1 and when Z5 or Z6 is any of the groups of the formulae (IV)-(VI), given and defined above, f or g respectively is zero;
each of c and e, independently, is zero or 1-4;
d is 1 or 2;
each R independently is as defined above;
each of Ar1 and Ar2 independently is an optionally substituted aryl group; and
each of R3 and R4 is as defined above.
In a dye of the formula (XVIII), each of Z5 and Z6 may be the same group 
wherein X, Y and n are as defined above.
Alternatively, one of Z5 and Z6 may be a group of the formula (I), given and defined above, and the other of Z5 and Z6 may be selected from groups of the formulae (II) and (III), given and defined above. In such a dye it is preferred that one of Z5 and Z6 is a group of the formula (I), given and defined above, and the other of Z5 and Z6 is a group of the formula (II).
Another especially preferred range of disazo dyes has the formula 
wherein:
B is a hydrocarbon bridging group as defined above, and preferably an optionally substituted aryl group;
one of G1 and G2 is OH and the other is NH2;
each of X, Y, Y1, Ar1, Ar2, R3, R4, R5, c, d and e is as defined above.
In a dye of the formula (XVIII), one of Z5 and Z6 may be a group 
wherein:
X, Y and n are as defined in claim 1 and the other of Z5 and Z6 is the group xe2x80x94SO2CH2CH2OSO3H or xe2x80x94SO2CHxe2x95x90CH2.
Typically such a dye has the formula 
wherein
G3 is C2H4OSO3H or a salt thereof or xe2x80x94CHxe2x95x90CH2;
G1 and G2 are as defined above;
R4 and d are as defined above; and
each of h and i, independently, is zero, 1 or 2.
A more preferred range of such dyes has the formula 
where each of G1 G2 and G3 is as defined above.
When the chromophore D is an anthraquinone, a preferred anthraquinone group is of the Formula (XII) (or a salt thereof). 
wherein the anthraquinone nucleus optionally contains a sulphonic acid group in the 5-, 6-, 7-, or 8-position and V is a divalent organic linking group, preferably of the benzene series.
V is a bridging group B, preferably phenylene, diphenylene, or 4,4xe2x80x2-divalent stilbene or azobenzene radicals which are optionally sulphonated. It is preferred that V contains one sulphonic acid group for each benzene ring present therein.
A preferred anthraquinone dye of has the formula
DAxe2x80x94L3xe2x80x94Arxe2x80x94L2xe2x80x94Z2xe2x80x94L1xe2x80x94Z1
wherein:
DA is an anthraquinone chromophore;
L3 is a linking of the formula (VII)1, given and defined above;
Ar is an optionally substituted aryl group; and
each of Z1, Z2, L1 and L2 is as defined above.
More preferably each of L1 and L2 independently, is a linking group of the formula (VII)1, (VII)2 or (VII)3, given and defined above; and still more preferably, each of L1 and L2, independently is a group of the formula (VII)3, given and defined above, in which B is an optionally substituted aryl group.
When the chromophore D is a phthalocyanine, a preferred phthalocyanine group is of the Formula (XIII) (or a salt thereof). 
wherein Pc is a metallo-phthalocyanine nucleus, preferably copper or nickel phthalocyanine; L is as hereinbefore defined; each W independently is a hydroxy or a substituted or unsubstituted amino group, V1 is a divalent organic linking group, preferably a C1-4-alkylene or phenylene linking group; and a and b are each independently 1, 2 or 3 provided that a+b is not greater than 4.
Preferably such a metal phthalocyanine dye has the formula 
wherein:
Cu Pc is a copper phthalccyanine chromophore;
x+y+zxe2x89xa64;
each of R21 and R23, independently is hydrogen or optionally substituted C1-4alkyl;
B is a hydrocarbon bridging group; and
Z1 Is as defined above.
When the chromophore D is a triphenodioxazine a preferred triphenodioxazine group is of the Formula (XIV) (or a salt thereof). 
wherein:
each Y1 independently is a covalent bond, C2-4-alkylene phenylene or sulphophenylene;
U1 is H or SO3H; and
T1 and T2 are halo, especially chloro, C1-4-alkyl, or alkoxy.
Each Y3 is preferably xe2x80x94C2H4xe2x80x94 or xe2x80x94C3H6xe2x80x94, U1 is preferably SO3H and T1 and T3 are preferably Cl, methyl or ethyl.
Preferably such a triphendioxazine dye has the formula
Z1xe2x80x94L1xe2x80x94[Z3xe2x80x94L3]q xe2x80x94DTxe2x80x94[Z4]rxe2x80x94L2xe2x80x94Z2
wherein:
DT is a triphendioxazine chromophore; each of L2, L3 and L4, independently, is a linking group of the formula (VII)1, (VII)2 or (VII)3, given and defined above;
each of Z2, Z3 and Z4 is a reactive group selected from groups of the formulae (I)-(III), given and defined above;
each of q and z is zero or 1; and
each of Z1 and L1 is as defined above.
In such a dye, Z2 is preferably a group of the formula (I), given and defined above and each of Z3 and Z4 is a group of the formula (II), given and defined above; and each of L1, L2, L3 and L4 is preferably a group of the formula (VII)3, given and defined above.
When the chromophore D is a formazan, a preferred group is of the Formula (XV) (or a salt thereof). 
wherein:
X1 is H, SO3H or Cl; and
each r independently has a value of 0, 1 or 2.
provided that the formazan group has at least one, and preferably at least two, sulpho groups.
It is preferred that each r has a value of 1.
Preferably such a formazan dye has the formula
[ZA]axe2x80x94DFxe2x80x94Lxe2x80x94ZBxe2x80x94L1xe2x80x94Z1
wherein:
DF is a formazan chromophore;
one of ZA and ZB is a group Z2, given and defined above;
each of L3 and L4 is a linking group of the formula (VII)1, (VII)2 or (VII)3, given and defined above;
each of Z1 and L1 is as defined above;
xcex1 is zero or 1;
ZA is selected from groups of the formulae (IV)-(VI), given and defined above; and
ZB is selected from groups of the formulae (I)-(III); given and defined above.
According to one process aspect, the invention provides a process for preparing a dye of the formula
Z2xe2x80x94L1xe2x80x94Dxe2x80x94L2xe2x80x94Z2xe2x80x83xe2x80x83(VIII)1
wherein:
D is a chromophore;
each of L1 and L2 independently, is N(R);
each R, independently, is hydrogen or C1-4alkyl;
each of Z1 and Z2 is a group 
in which:
n is 1 or 2
Xn or each X independently, is an electron withdrawing group; and
Y is a halogen atom, which process comprises reacting a chromophoric compound of the formula (XX)
H(R)Nxe2x80x94Dxe2x80x94N(R)Hxe2x80x83xe2x80x83(XX)
wherein each of D and R is as defined above, with at least two moles, per mole of the chromophoric compound of the formula (XX), of a dihalobenzene component comprising at least one dihalobenzene compound of the formula (XXI) 
wherein each of X, Y and n is as defined above, to obtain the dye of the formula (VIII)1.
When the dye is of the formula (XVIII) given above, the chromophoric compound of the formula (XX) can be prepared by protecting one amino group of a phenylene diamine sulphonic acid and then diazotising this and coupling a first portion of the diazotised phenylene diamine sulphonic acid to the naphthalene nucleus under acid conditions so as to couple or, to the benzene ring of the naphthalene nucleus containing an amino group and then taking a second portion of the same diazotised and protected phenylene diamine sulphonic acid compound referred to above (or a different such compound) and coupling this under neutral or alkaline conditions to the benzene ring of the naphthalene nucleus containing a hydroxyl group to obtain a diamine dyestuff having respective protected amino groups. The protective group can then be removed by hydrolysis.
According to another process aspect, the invention provides a process for preparing a dye of the formula (VIII)1
Z1xe2x80x94L1xe2x80x94Dxe2x80x94L2xe2x80x94Z2xe2x80x83xe2x80x83(VIII)2
wherein:
D is a chromophore;
each of L1 and L2 independently, is N(R);
each R, independently, is hydrogen or C1-4alkyl;
Z1 is a group 
in which:
n is 1 or 2
X, or each X independently, is an electron withdrawing group; and
Y is a halogen atom; and
Z2 is selected from the groups (II) and (III) defined above;
which process comprises reacting a chromophoric compound of the formula (XX)
H(R)Nxe2x80x94Dxe2x80x94N(R)Hxe2x80x83xe2x80x83(XX)
wherein each of D and R is as defined above, with one mole, per mole of the chromophoric compound of the formula (XX), of each of
(a) a dihalobenzene compound of the formula (XXI) 
wherein each of Z, X, Y and n is as defined above; and
(b) a compound selected from 
wherein:
m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, D is 0;
Y2, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group; and
T is C1-4alkoxy, C1-4thioalkoxy or N(R1)(R2), in which each of R1 and R2 independently is hydrogen, optionally substituted C1-4alkyl or optionally substituted aryl;
x is 1, 2 or 3; y is zero, 1 or 2; and x+yxe2x89xa63;
Y2, or each Y1 independently, is a halogen atom or an optionally substituted pyridinium group;
U or each U independently, is C1-4alkyl or C1-4alkylsulphonyl; and
Y is as defined above;
the said reactions of the compound of the formula (XX) with each of the respective compounds of the formulae (XII) and (XIII) being carried out simultaneously or one before the other, in either order, to obtain a of the formula (VIII)2.
According to yet another process aspect, the invention provides a process for preparing a dye of the formula (VIII)3
Z1xe2x80x94L1xe2x80x94Dxe2x80x94Z2xe2x80x83xe2x80x83(III)3
wherein:
D is a chromophore
L1 is N(R), in which R is hydrogen or C1-4alkyl;
Z1 is a group 
in which n is 1 or 2; X, or each X independently, is an electron withdrawing group; and Y is a hydrogen atom; and Z2 is a group of the formula (IV)
xe2x80x94SO2 CH2 CH2 X1xe2x80x83xe2x80x83(IV)
wherein X1 is an eliminatable group;
a group of the formulaxe2x80x83xe2x80x83(V)
xe2x80x94SO2 (CH2)2 CHxe2x95x90CH2(V)
wherein z is zero or 1; and
a group of formulaxe2x80x83xe2x80x83(VI)
xe2x80x94Wxe2x80x94C(R10)xe2x95x90CH2xe2x80x83xe2x80x83(VI)
wherein:
R10 is hydrogen, C1-4alkyl or halogen; and
W is xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94N(R11)C(xe2x95x90O)xe2x80x94 in which R11 is hydrogen or C1-4alkyl;
which process comprises reacting a chromophoric compound of the formula (XXIV)
H(R)Nxe2x80x94Dxe2x80x94Z2xe2x80x83xe2x80x83(XXIV)
wherein D and Z2 are as defined above, with a dihalobenzene compound of the formula (XXI) 
wherein each of X, Y and n is as defined above, to obtain the dye of the formula (VIII)3.
Although dye formulae have been shown in the form of their free acid in this specification, the invention also includes dyes and processes using dyes in the salt form, particularly their salts with alkali metals such as the potassium, sodium, lithium or mixed sodium/lithium salt and their salts with tetraalkylammonium ions.
The dyes may be used for dyeing, printing or ink-jet printing, for example, of textile materials and paper.
The process for colouration is preferably performed at a pH of 7.1 to 13, more preferably 10 to 12, pH levels above 7 can be achieved by performing the process for colouration in the presence of an acid-binding agent.
The substrate may be any of a textile material, leather, paper, hair or film, hot is preferably a natural or artificial textile material containing amino or hydroxyl groups, for example textile material such as wool, silk, polyamides and modified polyacrylonitrile fibres, and more preferably a cellulosic material, especially cotton, viscose and regenerated cellulose, for example, that commercially available as Tencel. For this purpose the dyes can be applied to the textile materials at a pH above 7 by, for example, exhaust dyeing, padding or printing, including ink-jet printing. Textile materials are coloured bright shades and possess good fastness to light and wet treatments such as washing.
The new dyes are particularly valuable for colouring cellulosic textile materials. For this purpose, the dyes are preferably applied to the cellulosic textile material at a pH above 7 in conjunction with a treatment with an acid binding agent.
Preferred acid-binding agents include alkali metal carbonates, bicarbonates, hydroxides, metasilicates and mixtures thereof, for example sodium bicarbonate, sodium carbonate, sodium metasilicate, sodium hydroxide and the corresponding potassium salts. The dyes benefit from the excellent build-up and high fixation.
At least for cellulosic materials, exhaust dyeing can be carried out at a relatively low temperature about 50-70xc2x0 C., especially about 60xc2x0 C.
The new dyes can be applied to textile material containing amine groups, such as wool and polyamide textile materials, from a neutral to mildly alkaline dyebath. The dyeing process ran be carried out at a constant or substantially constant during the dyeing process, or if desired the pH of the dyebath can be altered at any stage of the dyeing process.
The dyes may be in a liquid form, or solid form, for example in granular or powdered form.
We find surprisingly that such dyes give a much higher build up, as compared with known dyestuffs, particularly in warm dyeing applications at about 60xc2x0 C.
In addition, a wide selection of dye backbones is possible, giving the potential to provide high fastness dyes.
Dyes embodying the invention are especially useful for application to substrates by ink-jet technologies. Substrates which are particularly useful are cellulosic textiles and paper.
The dye used in the ink is preferably purified by removal of substantially all the inorganic salts and by-products which are generally present in a commercial dye at the end of its synthesis. Such purification assists in the preparation of a low viscosity aqueous solution suitable for use in an ink jet printer.
To assist in the achievement of heavy depths of shades the dye should preferably have a water-solubility of at least 5%, and more preferably from 5% to 25%, by weight. Solubility of the dye can be enhanced converting the sodium salt, in which form it is normally synthesised, either partially or wholly, into the lithium or ammonium salt. Purification and ion exchange can conveniently be effected by use of membrane separation processes which permit the separation of unwanted inorganic materials and by-products directly from an aqueous solution or dispersion of the dye by partial or complete exchange of the counter-ion. The ink preferably contains, up to 20% by weight of dye and more preferably from 2% to 10%, especially from 3% to 8%.
The ink may also contain a humectant, which may also function as a water miscible solvent, which preferably campfires a glycol or dihydroxyglycolether, or mixture thereof, in which one or both hydroxy groups are secondary hydroxy groups, such as propane-1,2-diol,butane-1,3-diol and 3-(3-hydroxy-prop-2-oxy)propan-2-ol.
Where the humectant has a primary hydroxy group this is preferably attached to a carbon atom adjacent to a carbon atom, carrying a secondary or tertiary hydroxy group. The humectant may comprise up to a total of 10% by weight of a polyol, especially a glycol or dihydroxyglycolether, having two or more primary hydroxy groups, such as ethyleneglycol, propane-1,3-diol,butane-1,4-diol,2-(2-hydroxyethoxy)ethanol and 2-(2-[2-hydroxyethoxy)ethanol and/or an alcohol with a primary hydroxy group, such as ethanol,n-proponol and n-butanol. However, it preferably contains not more than 5% by weight, and is more preferably free from, such compounds. In the context of the humectant, the term xe2x80x9calcoholxe2x80x9d means a compound having only one hydroxy group attached to an aliphatic carbon atom. The ink preferably contains from 5% to 25%, by weight, more especially from 10% to 20%, of humectant.
If desired, the ink may be buffered to a pH from 5 to 8, especially to a pH from 6 to 7, with a buffer such as the sodium salt of metanilic acid or an alkali metal phosphate, or di- or triethanolamine.
The ink preferably also contains one or more preservatives to inhibit the growth of fungi, bacteria and/or algae because these can block the jet of the ink jet printing equipment. Where the ink jet printing technique involves the charging and electrically controlled deflection of drops the solution preferably contains a conducting material such as an ionised salt to enhance the accumulation of charge on the crop. Suitable salts for this purpose are alkali metal salts of mineral acids. The remainder of the ink is preferably water, especially de-ionised water to avoid the introduction of impurities into the ink.
Especially preferred embodiments of the invention will now be described in more detail with reference to the following Examples in which all parts and percentages are by weight unless otherwise stated. Although preparation and dyeing with any single dye is exemplified, particular advantage could be seen when dyeing with mixtures of dyes.